CN107123808A - Lithium rechargeable battery - Google Patents

Lithium rechargeable battery Download PDF

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Publication number
CN107123808A
CN107123808A CN201710104673.5A CN201710104673A CN107123808A CN 107123808 A CN107123808 A CN 107123808A CN 201710104673 A CN201710104673 A CN 201710104673A CN 107123808 A CN107123808 A CN 107123808A
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China
Prior art keywords
active material
positive
rechargeable battery
electrode active
lithium rechargeable
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CN201710104673.5A
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Inventor
佐野笃史
大槻佳太郎
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TDK Corp
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TDK Corp
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Priority claimed from JP2016250325A external-priority patent/JP2017152362A/en
Application filed by TDK Corp filed Critical TDK Corp
Publication of CN107123808A publication Critical patent/CN107123808A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of quick charge at low temperature excellent lithium rechargeable battery.The lithium rechargeable battery of the present invention, which possesses in the positive pole with positive electrode active material layer, negative pole and electrolyte, above-mentioned positive electrode active material layer, contains Lia(M)b(PO4)cAs positive active material, wherein, M=VO or V, 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c≤3.3, further containing by fluorine element convert relative to positive electrode active material layer weight be 1~300ppm fluorine compounds.

Description

Lithium rechargeable battery
Technical field
The present invention relates to lithium rechargeable battery.
Background technology
All the time, LiCoO is used always as the positive electrode (positive active material) of lithium rechargeable battery2Or LiNi1/3Mn1/3Co1/3O2Deng lamellar compound or LiMn2O4Deng spinel compound.In recent years, with LiFePO4For generation The compound of the olivine-type structure of table attracts attention.Heat endurance under the known positive electrode high temperature with olivine structural Height, and it is safe.But, use LiFePO4Lithium rechargeable battery its charging/discharging voltage as little as 3.5V, and have Have the shortcomings that energy density is low.Therefore, as that can realize the phosphate positive electrode of high charging/discharging voltage, motion has LiCoPO4Or LiNiPO4Deng.
But, even if in the lithium rechargeable battery of these positive electrodes has been used, present situation is also that can not obtain fully Capacity.Even in phosphate positive electrode, being used as the compound for the charging/discharging voltage that can realize 4V grades, it is known to have There is LiVOPO4Or Li3V2(PO4)3Structure vanadium phosphate.Used these compounds as positive electrode active material situation Under, deposit the insufficient technical problem of quick charge characteristic at low temperature.Above-mentioned positive electrode is to for example following patent documents 1,2 In to quick charge in a low temperature of described in vanadium phosphate the problem of it is not on the books.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-68304 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-231206 publications
The content of the invention
The technical problem solved is wanted in invention
The present invention is in view of the invention that technical problem present in above-mentioned prior art is completed, its object is to provide one kind The excellent lithium rechargeable battery of quick charge under low temperature.
Solve the means of technical problem
In order to achieve the above object, lithium rechargeable battery involved in the present invention possesses with positive electrode active material layer Contain Li in positive pole, negative pole and electrolyte, above-mentioned positive electrode active material layera(M)b(PO4)c(M=VO or V, 0.9≤a≤ 3.3,0.9≤b≤2.2,0.9≤c≤3.3) as positive active material, further containing by fluorine element conversion relative to positive pole The weight of active material layer is 1~300ppm fluorine compounds.
By said structure, as the lithium rechargeable battery that the quick charge under low temperature is excellent.This is considered due to fluorine The decomposition and suppression of the above-mentioned positive active material of compound suppression and electrolyte are formed at the increase of the overlay film on interface.
In lithium rechargeable battery involved in the present invention, above-mentioned fluorine compounds are preferably lithium fluoride.
It is lithium fluoride by above-mentioned fluorine compounds, so that lithium fluoride specifically interacts with positive active material, and And suppress the decomposition of electrolyte, suppress to be formed at the increase of the overlay film at interface.
In addition, in lithium rechargeable battery involved in the present invention, above-mentioned fluorine compounds be preferably in from it is above-mentioned just The surface of pole active material to the region of 100nm depth.
Think by the fluorine compounds on the surface of positive active material be present in from the surface of above-mentioned positive active material to The region of 100nm depth, can more efficiently suppress the decomposition of electrolyte, and suppress to be formed at the increasing of the overlay film at interface Greatly.
Further, above-mentioned positive active material preferably comprises LiVOPO4Or Li3V2(PO4)3.Think by making so Positive active material, so as to specifically be interacted with fluorine compounds, and suppress the decomposition of electrolyte, suppress to be formed at The increase of the overlay film at interface.
Above-mentioned positive active material, contains LiNi preferably as the second positive active materialxCoyMnzMaO2(x+y+z+a= 1,0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1, M is the member selected from one or more of Al, Mg, Nb, Ti, Cu, Zn, Cr Element).
Above-mentioned positive active material contains 1 preferably with respect to the summation of positive active material and the second positive active material~ 30wt%.
As above-mentioned electrolyte, 4- fluorinated ethylene carbonates are preferably comprised.
Think by containing 4- fluorinated ethylene carbonates, so that Lia(M)b(PO4)c(M=VO or V, 0.9≤a≤3.3, The surface fluorination compound of 0.9≤b≤2.2,0.9≤c≤3.3) is stabilized, and promotes the mutual of positive active material and fluorine compounds Effect, and suppress to be formed at the increase of the overlay film at interface.
Above-mentioned negative pole is preferably comprised more than at least one of silicon, silica as negative electrode active material.
Contained by above-mentioned negative electrode active material more than at least one of silicon, silica, so as to carry out more Quick charge in a low temperature of good.
The effect of invention
By the invention it is possible to provide quick charge under low temperature excellent lithium rechargeable battery.
Brief description of the drawings
Fig. 1 is the schematic section of the lithium rechargeable battery involved by present embodiment.
Symbol description
10 ... positive poles；20 ... negative poles；12 ... positive electrode collectors；
14 ... positive electrode active material layers；18 ... barrier films；22 ... negative electrode collectors；
24 ... negative electrode active material layers；30 ... generating elements；50 ... casings
60th, 62 ... wires；100 ... lithium rechargeable batteries
Embodiment
Hereinafter, while one side is described in detail for the preferred embodiment of the present invention referring to the drawings.In addition, this hair It is bright to be not limited to following embodiment.In addition, in the inscape recorded below, including those skilled in the art are readily apparent that , substantially the same key element.Further, the inscape recorded below can be combined as.
(lithium rechargeable battery)
As shown in figure 1, the lithium rechargeable battery 100 involved by present embodiment possess generating element 30, containing lithium from The electrolyte solution of son, casing 50, the end electrical connection for housing power generation element 30 and electrolyte solution in a sealed state The cathode conductor 62 of the outside of casing, an end are protruded from negative pole 20 and the other end and is electrically connected to positive pole 10 and another One end protrudes from the positive wire 60 of the outside of casing, wherein, power generation element 30 possesses the negative pole 20 of tabular relative to each other And positive pole 10, the barrier film 18 for the tabular being adjacently configured between negative pole 20 and positive pole 10 of tabular.
Negative pole 20 has negative electrode collector 22, the negative electrode active material layer 24 being stacked on negative electrode collector 22.In addition, just Pole 10 has positive electrode collector 12, the positive electrode active material layer 14 being stacked on positive electrode collector 12.Barrier film 18 is lived positioned at negative pole Between property material layer 24 and positive electrode active material layer 14.
(first embodiment)
(positive electrode active material layer)
In positive electrode active material layer in the positive pole used in the lithium rechargeable battery of present embodiment, lived as positive pole Property material, contains Lia(M)b(PO4)c(M=VO or V, 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c≤3.3), enter one The weight walked relative to positive electrode active material layer contains 1~300ppm fluorine compounds.
In present embodiment, the fluorination that the above-mentioned positive electrode active material layer of lithium rechargeable battery contains 1~300ppm is closed Thing.It is preferably 10~250ppm scope as the content of fluorine compounds.More preferably 15~200ppm scope.
As the method containing fluorine compounds, have synthesis when into raw material the method for mixed fluoride compound, by wet type Method, dry process, vapor phase method etc. are adsorbed in the method on the positive active material surface after synthesis.
It is known as the Li of the vanadium phosphate of above-mentioned positive active materiala(M)b(PO4)c(M=VO or V, 0.9≤a≤ 3.3,0.9≤b≤2.2,0.9≤c≤3.3), it can be synthesized by synthesis in solid state, Hydrothermal Synthesiss, carbothermic method etc..Its In, the vanadium phosphate particle diameter made of hydrothermal synthesis method is small, and multiplying power property has the tendency of excellent, to be made of hydrothermal synthesis method phosphoric acid Vanadium is preferably as positive active material.It is considered the vanadium phosphate particle diameter, crystal shape, crystallization due to being synthesized by hydrothermal synthesis method Property etc. key element be adapted to improve multiplying power property.
In above-mentioned positive electrode active material layer contained above-mentioned fluorine compounds be preferably lithium fluoride, fluorination phosphorus, fluorinated phosphate lithium, Fluorinated phosphate vanadium, fluorinated phosphate vanadium lithium etc., are particularly preferred and exist as lithium fluoride.Think that lithium fluoride can effectively suppress electricity The decomposition and increase of solution liquid are formed at the increase of the overlay film at interface.
It is preferred that to be present in above-mentioned positive electrode active material layer surface attached for fluorine compounds contained in above-mentioned positive electrode active material layer Closely, and it is preferably in the depth from a surface to 100nm.Further preferably it is present in the depth from a surface to 80nm, especially It is preferably in 70nm depth.Think by fluorine compounds be present in the range of this so as to suppress electrolyte decomposition and Suppression is formed at the increase of the overlay film at interface.The existing forms of fluorine compounds are not particularly limited, and are uniform membranaceous or inequality Even island.
(detections of fluorine compounds in the depth direction)
Contained fluorine compounds can be used in above-mentioned positive electrode active material layer is with X-ray photoelectron spectroscopy (XPS) The existing analysis method represented is determined.Row element point can be entered in the depth direction from the surface of positive electrode active material layer Analysis, and determine the presence or absence of fluorine compounds.
(measure of Oil repellent)
Contained Oil repellent can use the chromatography of ions to be measured in above-mentioned positive electrode active material layer.Now, in advance Binder Composition is gone out so as to the content for the fluorine for determining the fluorine compounds from target using the solvent of acid etc..Afterwards, By and with the weight of Binder Composition that eliminates, so as to be scaled containing for fluorine contained in positive electrode active material layer Amount.
Think that the lithium rechargeable battery involved by present embodiment can carry out the mechanism of the quick charge under low temperature such as It is lower described.It is considered due to by Lia(M)b(PO4)c(M=VO or V, 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c There is lithium fluoride on≤surface 3.3), so that lithium fluoride suppresses Lia(M)b(PO4)cDecomposition and suppression with electrolyte are formed at The increase of overlay film on interface.Above-mentioned positive active material in the present embodiment contains LiVOPO4Or Li3V2(PO4)3's In the case of, the effect of the quick charge especially under low temperature is notable.
(second embodiment)
In lithium rechargeable battery involved by present embodiment, contain Li as positive active materiala(M)b(PO4)c(M =VO or V, 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c≤and 3.3) as the first positive active material, further contain Fluorine compounds, herein on, merge as the second positive active material and contain the positive active material that uses all the time.
As the second positive active material, for example, oxidate for lithium, lithium sulfide or the interlayer containing lithium can be enumerated They two or more, can be used in mixed way by lithium-containing compound of compound etc. etc..
Especially, from the viewpoint of energy density, preferred formula LixMO2Represented lithium composite xoide, Huo Zhehan The intercalation compound of lithium.In addition, M is preferably more than a kind of transition metal, specifically, be preferably selected from Co, Ni, Mn, Fe, It is at least one kind of in V, Ti.X is different according to the charging and discharging state of battery, usually the value in the range of 0.05≤x≤1.10.
In addition, other galaxite (LiMn that can also be used with spinel structure2O4) or with olivine-type structure LiFePO4 (LiFePO4) etc..
Specifically, cobalt acid lithium (LiCoO can be enumerated2), lithium nickelate (LiNiO2)、LiNixCoyMnzMaO2(x+y+z+a =1,0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1, M are selected from one or more of Al, Mg, Nb, Ti, Cu, Zn, Cr Element), olivine-type LiMPO4(wherein, M is the member selected from one or more of Co, Ti, Mn, Fe, Mg, Nb, Ti, Al, Zr Element), LiNixCoyAlzO2(0.9<x+y+z<1.1) etc..In addition, these materials are not limited to, as long as other electrochemically insert The cathode active material for entering or departing from lithium ion is all not particularly limited.
Wherein, from the viewpoint of it can obtain high-energy-density, the second positive active material is preferably used LiNi0.33Co0.33Mn0.33O2、LiNi0.5Mn0.2Co0.3O2、LiNi0.85Co0.10Al0.05O2Deng lithium composite xoide.
Preferably with respect to positive active material and the second positive-active in positive active material involved by present embodiment The content of the positive active material of the summation of material is 1~30wt%.In addition, more preferably 3~21wt%, more preferably For 5~16wt%.
Think by the summation relative to positive active material and the second positive active material, within the above range containing just Pole active material, from the high energy density without damaging the second positive active material, by being used as positive active material Lia(M)b(PO4)c(there is fluorination on M=VO or V, the surface of 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c≤3.3) Lithium, Li is suppressed so as to fully obtain lithium fluoridea(M)b(PO4)cWith the decomposition of electrolyte, and suppress be formed at interface The effect of the increase of overlay film.
(positive active material, the content of the second positive active material)
The content of positive active material and the second positive active material can use X-ray diffraction measure (XRD) and Inductively coupled plasma atomic emission spectrometry (ICP-AES) etc. is determined.In the positive active material with XRD determining and Positive electrode active material layer containing the second positive pole, and after identifying positive active material and the second positive active material, make Transition metal contained in positive electrode active material layer is determined with ICP-AES etc., and by being used as positive active material And second positive active material convert so as to calculating respective content.
Positive electrode active material layer 14 contains above-mentioned positive active material and conductive auxiliary agent.As conductive auxiliary agent, it can enumerate The carbon material of carbon black class etc., the metal powder of copper, nickel, stainless steel, iron etc., the mixture of carbon material and metal powder, as ITO Electroconductive oxide.Carbon material preferably comprise the carbon that tap density is 0.03~0.09g/ml and tap density be 0.1~ 0.3g/ml carbon.Positive electrode active material layer can contain the binding agent for bonding active material and conductive auxiliary agent.Positive active material Layer 14 can be by the LiVOPO that will be obtained containing the manufacture method involved by above-mentioned present embodiment4, binding agent, solvent and lead The coatings of electric auxiliary agent are formed in the process on positive electrode collector 12.
In addition, in the case where merging containing the second positive active material, second can be further mixed in above-mentioned operation Positive active material.
, can be before hybrid adhesive, solvent, conductive auxiliary agent in the case where mixing the second positive active material, will Positive active material and the second positive active material dispersion mixing.
The method of scattered, mixed cathode active material and the second positive active material is not particularly limited, and can use addition Dry type mixing that the jar mill of zirconia ball or alumina balls is carried out, the dry type mixing of mixing and kneading machine used, filled by fluidized bed Put the known method all the time such as mixing of progress.
(electrolyte)
As the electrolyte of the lithium rechargeable battery involved by present embodiment, 4- fluorinated ethylene carbonates are preferably comprised (FEC).FEC addition integrally adds 0.1~35 weight % preferably with respect to electrolyte, can quickly be filled at low temperature Electricity.
In addition, as the electrolyte of present embodiment, can suitably use and be dissolved in nonaqueous solvents using lithium salts as solute The electrolyte solution obtained in (organic solvent).As lithium salts, for example, it can use LiPF6、LiClO4、LiBF4、LiAsF6、 LiCF3SO3、LiCF3、CF2SO3、LiC(CF3SO2)3、LiN(CF3SO2)2、LiN(CF3CF2SO2)2、LiN(CF3SO2) (C4F9SO2)、LiN(CF3CF2CO)2, the salt such as LiBOB.In addition, these salt can be used alone, can also and with 2 kinds with On.
In addition, as organic solvent, for example, it is preferable to which propene carbonate, ethylene carbonate and carbonic acid diethyl can be enumerated Ester, dimethyl carbonate, methyl ethyl carbonate etc..These can be used alone, and can also mix two or more to make with arbitrary ratio With.In order to which fluorine compounds are stabilized in positive active material, fluorochemical can be contained in above-mentioned electrolyte.
In addition, in the present embodiment, electrolyte can also be to be obtained in addition to liquid by adding gelating agent Gel-like electrolyte.In addition, alternative electrolyte, can also containing solid electrolyte (by solid macromolecule electrolyte or from The electrolyte that sub- conductive inorganic is constituted).
(negative electrode active material)
As negative electrode active material, can for example enumerate native graphite, Delanium, difficult graphitized charcoal, easy graphitized charcoal, Metal or alloy that the carbon material of easy fired charcoal etc., Al, Si, Sn, Ti etc. can be closed with lithiumation, with SiOx(1<x≤2)、SnOx (1<Amorphous compound of the oxides such as x≤2) as main body, lithium titanate (Li4Ti5O12)、TiO2Deng.
As the negative electrode active material of the lithium rechargeable battery involved by present embodiment, Si or SiO is preferably comprisedx(1 <X≤2) etc. is selected from silicon, at least one of silica, and thus the charge characteristic in a low temperature of battery is more excellent.This be considered by In in order to suppress containing Lia(M)b(PO4)cPositive electrode surface electrolyte decomposition and suppression is formed at overlay film on interface Increase and prevent the analyte of positive pole to negative pole swimming.
As the negative electrode active material contained by negative electrode active material layer 24, can possess above-mentioned material, and the negative pole Active material can be bonded by binding agent.Negative electrode active material 24 is identical with the situation of positive electrode active material layer 14, Ke Yitong Cross and form the coatings containing negative electrode active material etc. in the process on negative electrode collector 22.
(barrier film)
In addition, barrier film 18 can be formed by the porous structure of electrical insulating property, for example, it can enumerate by polyethylene, polypropylene Or the stretched film of the mixture of the individual layers of film, layered product or above-mentioned resin that constitutes of polyolefin or by selected from cellulose, The fabric nonwoven cloth that at least one kind of constituent material in polyester and polypropylene is constituted.
<Casing>
Casing 50 has laminated body 30 and electrolyte solution in its inner sealing.As long as casing 50 can prevent electrolyte molten Liquid is spilt to outside or moisture etc. is just not particularly limited from the object inside outside intrusion lithium rechargeable battery 100.Example Such as, as casing 50, as shown in Figure 1, it is possible to use coat the metal laminate of metal foil 52 from both sides with polymeric membrane 54 Film.Aluminium foil can be for example utilized as metal foil 52, the film of polypropylene etc. can be utilized as synthetic resin film 54.For example, making For the high macromolecule of the material preferably fusing point of the polymeric membrane 54 in outside, such as PET (PET), polyamide Deng being preferably polyethylene (PE), polypropylene (PP) etc. as the material of the polymeric membrane 54 of inner side.
Wire 60,62 is formed by conductive materials such as aluminium.
(gas generated measure)
In by lithium rechargeable battery obtained above, the situation of the generation rate of the gas in the case where determining charged state Under Archimedes method can be used to determine.Specifically, it is that battery is sunken in pure water, determines buoyancy, and by discharge The volume of water is calculated as gas generated.
More than, the preferred embodiment for lithium rechargeable battery involved in the present invention has been carried out in detail Illustrate, but the present invention is not limited to above-mentioned embodiment.
Embodiment
Hereinafter, the present invention has been more specifically described based on embodiment and comparative example, but the present invention be not limited to it is following Embodiment.
(embodiment 1)
[making of evaluation electricity pool]
By V2O5, LiOH and H3PO4Mol ratio be set to about 1:2:2, and heating 8 is small at 160 DEG C in closed container When, and will be burnt till 4 hours at obtained lotion in atmosphere 600 DEG C.It is β types LiVOPO to understand the particle so obtained4。
By LiVOPO4Particle, acetylene black (the electrochemically FX-35 of industry manufacture), Ketjen black (Ketjenblack The EC600JD of International Co. manufactures) with 80:5:5 weight passes through planet-shaped ball mill than weighing to it Carry out the mixed processing of 31 minutes.The speed setting of planet-shaped ball mill is 550rpm.
Using thus obtained mixture and it is used as the Kynoar (KF7305 that PVDF, Wu Yuhua length of schooling are made) of binding agent The mixture obtained after mixing, which is scattered in the pyrrolidones of 1- methyl -2 (NMP) as solvent, has modulated slurry.In addition, will slurry The weight ratio of mixture and PVDF in material is adjusted to 90:10.Lithium fluoride be with the addition of to relative to positive active material, binding agent Total weight with conductive auxiliary agent is 0.005 weight %.The slurry is coated on as on the aluminium foil of collector, and done After dry, rolling is carried out, the positive pole for foring active material layer has been made.
Next, as negative pole by the Delanium FSN of manufacture (BTR Inc.) and the N- methyl of Kynoar (PVDF) The 5wt% solution of pyrrolidones (NMP) is with Delanium:Kynoar=93:7 ratio is mixed, and is made The coating of pulp-like.Using coatings on the copper foil as collector, and negative pole is made by drying, rolling.
Positive pole, negative pole are subjected to lamination to clip the barrier film being made up of microporous polyethylene film between it, and obtained Laminated body (ferritic).The laminated body is fitted into aluminium lamination press mold bag.Electrolyte is by ethylene carbonate (EC), diethyl carbonate (DEC) with volume ratio 3:7 are mixed, and LiPF has been dissolved in the way of as 1mol/L as support salt6。
In the aluminium lamination press mold bag of laminated body is enclosed, it is filled with after above-mentioned electrolyte, carries out Vacuum Package, makes The evaluation electricity pool of embodiment 1.
(embodiment 2~6, comparative example 3)
In addition to the addition for changing lithium fluoride, other same methods all with embodiment 1 made embodiment 2~ 6 and the evaluation electricity pool of comparative example 3.
(embodiment 7~12, comparative example 2)
Make and lithium fluoride is not added in positive pole, and with the addition of the battery of 4- fluorinated ethylene carbonates in the electrolytic solution. In addition, method similarly to Example 1 has made the evaluation electricity pool of embodiment 7~12 and comparative example 2.
(embodiment 13)
The graphite for being mixed with 90 weight %, the negative electrode active material system of 10 weight % silicon are used as negative electrode active material Negative pole is made.In addition, method similarly to Example 9 has made the evaluation electricity pool of embodiment 13.
(embodiment 14~19)
Silicon is used to make negative pole as negative electrode active material.In addition, made with the same method of embodiment 1~6 The evaluation electricity pool of embodiment 14~19.
(embodiment 20~25)
Li is used as positive active material3V2(PO4)3Positive pole is made.In addition, it is same with embodiment 7~12 Method has made the evaluation electricity pool of embodiment 20~25.
(embodiment 26)
The graphite for being mixed with 90 weight %, the negative electrode active material system of 10 weight % silicon are used as negative electrode active material Negative pole is made.In addition, method similarly to Example 24 has made the evaluation electricity pool of embodiment 26.
(embodiment 27)
Li is used as positive active material0.9VOPO4Positive pole is made.In addition, method similarly to Example 18 The evaluation electricity pool of embodiment 27 is made.
(embodiment 28,29)
LiVOPO has been used as positive active material4, used as the second positive active material LiNi0.33Mn0.33Co0.33O2(NMC has been recorded in table), using mixing ratio as 7:3 or 3:They are mixed and use the mixing by 7 Thing has made positive active material, and positive pole has been made using the positive active material.In addition, with same with embodiment 9 Method has made the evaluation electricity pool of embodiment 28,29.
(embodiment 30)
Used as positive active material with mixing ratio 3:7 are mixed with LiVOPO4And LiNi0.33Mn0.33Co0.33O2Positive pole Active material, positive pole has been made using the positive active material.In addition, reality has been made in the method same with embodiment 13 Apply the evaluation electricity pool of example 30.
(comparative example 1)
Other same methods all with embodiment 1 have made the evaluation electricity consumption of comparative example 1 in addition to without lithium fluoride Pond.
(comparative example 4)
It is other in addition to adding lithium fluoride not into electrolyte that all with comparative example 1, same method has made comparative example 4 Evaluation electricity pool.
(embodiment 31,32 and comparative example 5)
In addition to the addition for changing lithium fluoride, other all with embodiment 14, same method has made embodiment 31st, 32 and comparative example 5 evaluation electricity pool.
(embodiment 33 and comparative example 6)
In addition to the addition for changing FEC, other same methods all with embodiment 20 made embodiment 33 with And the evaluation electricity pool of comparative example 6.
(embodiment 34~40, comparative example 7,8)
In addition to the addition for changing FEC, other same methods all with embodiment 29 made embodiment 34~ 40 and the evaluation electricity pool of comparative example 7,8.
(measure of fluorine compounds)
In each positive pole obtained by the method for embodiment 1~40 and comparative example 1~8, by from positive electrode active material The surface of matter layer carries out elementary analysis with XPS, so as to confirm the surface from positive electrode active material layer of each positive pole to depth side The presence or absence of upward fluorine compounds.Untill from the surface of each positive electrode active material layer to the depth for being capable of detecting when fluorine compounds It is used as the domain of the existence of fluorine compounds.In addition, the mark for not detecting fluorine compounds is (No Detected).
(measure of Oil repellent)
In each positive pole obtained by the method for embodiment 1~40 and comparative example 1~8, surveyed using the chromatography of ions The content of fluorine contained in positive electrode active material layer is determined.
(measure of the quick charge characteristic under low temperature)
The electric current circulated at 0 DEG C relative to battery capacity equivalent to 2C, and determine the time of charging complete.Charging Carried out by constant current constant voltage charging (CCCV chargings), and the conduct when reaching the 1/20C current value of battery capacity Termination condition.Since time as the charging interval untill reaching termination condition charging is evaluated.In addition, by electricity Current density 1C is set to 160mAh/g, and charging voltage is set into 4.2V (vs.Li/Li+) be measured.
The evaluation electricity pool made by embodiment 1~40 and the method for comparative example 1~8 is determined under these conditions Fast charging and discharging characteristic, by the average value of the result after being evaluated respectively using n=5 as each battery fast charging and discharging characteristic.
(gas generated measure)
In embodiment 1~40 and the evaluation electricity pool of comparative example 1~8, the quick charge characteristic under low temperature is determined Afterwards, evaluation electricity pool is discharged by constant current discharge (CV electric discharges).In addition, discharge voltage is set as 3.0V (vs.Li/Li+), current density is set as equivalent to 0.5C.The gas generated use A Ji meter of evaluation electricity pool after electric discharge Moral method is determined.
The result of the embodiment 1~40 obtained by these measure and comparative example 1~8 is shown in table 1 below.
【Table 1】
It can be seen from the result of above-mentioned table 1, the fast charging and discharging characteristic under evaluation battery low temperature in the present application is carried It is high.In addition, it was found from the result of comparative example 4, in the case of with the addition of fluorine compounds in the electrolytic solution, the quick charge and discharge under low temperature Electrical characteristics are not improved.This is considered due to different from making an addition to the situation in positive electrode active material layer, in positive active material The reason for fluorine compounds are not present in layer.
(embodiment 41~48, comparative example 9,10)
Except having used LiNi as the second positive active material0.85Co0.10Al0.05O2Beyond (NCA is designated as in table), its It has all made embodiment 41~48 with embodiment 29, embodiment 34~40 and the same method of comparative example 6,7 and compared The evaluation electricity pool of example 9,10.
By the side of the evaluation electricity pool made by embodiment 41~48 and the method for comparative example 9,10 similarly to Example 1 Method determines the gas generated of the evaluation electricity pool after fluorine compounds, the content of fluorine and low temperature charge characteristic are determined.
By the side of the evaluation electricity pool made by embodiment 41~48 and the method for comparative example 9,10 similarly to Example 1 Method determines fast charging and discharging characteristic, and the result after n=5 is evaluated respectively average value as each sample quick charge and discharge Electrical characteristics.
The result of the embodiment 41~48 obtained by these measure and comparative example 9,10 is shown in following table 2.
【Table 2】
According to the result of above-mentioned table 2, it is thus identified that also can same at low temperature fast even if changing the second positive active material Fast charge characteristic is improved.
(embodiment 49~57)
Except changing containing for summation of the positive active material relative to positive active material and the second positive active material Measure beyond (being designated as below " content of positive active material "), other all with embodiment 41, same method has made embodiment 49 ~57 evaluation electricity pool.
(measure of initial discharge capacity)
Initial discharge capacity is that after the quick charge characteristic under determining low temperature, evaluation electricity pool is passed through into constant current Electric discharge (CV electric discharges) is discharged.In addition, discharge voltage is set as 3.0V (vs.Li/Li+), current density is set as quite In 0.5C.By obtained by the gross weight of the capacity now obtained divided by respective positive active material and the second positive active material The value arrived as positive pole primary charging capacity (mAhg-1).In addition, current density is set to 1C for 160mAh/g to be surveyed It is fixed.
By the way that the evaluation electricity pool of embodiment 49~57 and embodiment 41 is carried out into discharge and recharge under these conditions, so that Determine the initial discharge capacity of each evaluation electricity pool, and by each using the average value of the n=5 results evaluated as respective Initial discharge capacity.
The evaluation electricity pool made by the method for embodiment 49~57 is determined soon in method similarly to Example 1 It is fast charge-discharge characteristic, gas generated.
The result for the embodiment 49~57 that measure by these is obtained is shown in table 3 below.
【Table 3】
It can be seen from the result of above-mentioned table 3, in the case where the content of positive active material is 1~30wt% scope, High initial discharge capacity is also taken into account outside quick charge characteristic at low temperature.

Claims (8)

1. a kind of lithium rechargeable battery, wherein,
The lithium rechargeable battery possesses：Positive pole, negative pole and electrolyte with positive electrode active material layer,
Contain Li in the positive electrode active material layera(M)b(PO4)cAs positive active material,
Wherein, M=VO or V, 0.9≤a≤3.3,0.9≤b≤2.2,0.9≤c≤3.3,
Further contain by fluorine element conversion relative to the fluorine compounds that the weight of positive electrode active material layer is 1~300ppm.
2. lithium rechargeable battery as claimed in claim 1, wherein,
The fluorine compounds are lithium fluoride.
3. lithium rechargeable battery as claimed in claim 1 or 2, wherein,
During the fluorine compounds are present in from the surface of the positive electrode active material layer to the region of 100nm depth.
4. such as lithium rechargeable battery according to any one of claims 1 to 3, wherein,
The positive active material contains LiVOPO4Or Li3V2(PO4)3。
5. such as lithium rechargeable battery according to any one of claims 1 to 4, wherein,
In the positive electrode active material layer, contain LiNixCoyMnzMaO2As the second positive active material, wherein, x+y+z+a= 1,0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1, M is the member selected from one or more of Al, Mg, Nb, Ti, Cu, Zn, Cr Element.
6. lithium rechargeable battery as claimed in claim 5, wherein,
In the positive electrode active material layer, the positive active material is relative to the positive active material and second positive pole The summation of active material contains 1~30wt%.
7. such as lithium rechargeable battery according to any one of claims 1 to 6, wherein,
Contain 4- fluorinated ethylene carbonates as the electrolyte.
8. such as lithium rechargeable battery according to any one of claims 1 to 7, wherein,
In the negative pole, containing being used as negative electrode active material selected from one or more of silicon, silica.
CN201710104673.5A 2016-02-25 2017-02-24 Lithium rechargeable battery Pending CN107123808A (en)

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